Catalyst system comprising an organo-aluminum,a metal salt of a beta-diketone and water



United States Patent .Int. Cl. C08g 23/06 US. Cl. 252-431 7 ClaimsABSTRACT OF THE DISCLOSURE A polymerization catalyst comprising (a) anorganoaluminum compound, (b) a metal salt of a beta-diketone, and (c)water.

This is a divisional application of patent application filed June 7,1965, Ser. No. 462,113, now United States Patent 3,396,125.

This invention relates to alkene oxide polymerization. In one aspect,this invention relates to catalyst systems for polymerizing epoxides. Inanother aspect, this invention relates to processes of polymerizingalkene oxides.

Several dilferent processes of polymerizing alkene oxides are describedin the patent art and in the technical literature. The catalyst systemsemployed in some of these processes include organoaluminum compounds ororganoaluminum compounds in admixture with a particular type of metalacetyl-acetonate. Other catalysts employed are organoaluminum compoundsin admixture With a chelating agent such as acetylacetone. The alkeneoxide polymers produced by the catalyst systems of the prior art rangein consistency from low molecular weight liquids to comparatively highmolecular weight waxy solids with almost no elastomeric properties. Aserious disadvantage with these catalyst systems insofar as alkene oxidepolymerization is concerned is the low monomer conversion associatedwith their use. Another shortcoming of the prior art processes andcatalyst systems for polymerizing alkene oxides is that rubbery polymersare ordinarily not produced.

According to this invention, these and other disadvantages of the priorart processes of polymerizing alkene oxides are overcome by providing anovel catalyst system comprising an organoaluminum compound, a metalsalt of a beta-diketone, and water. The alkene oxide polymers producedby the catalyst of this invention are high molecular Weight rubbers asevidenced by the high inherent viscosity of the product. A higherpolymerization rate is also made possible by means of the catalystsystem of this invention.

The organoaluminum component of the catalyst system can be atriorganoaluminum compound, an organoaluminum monohalide, organoaluminummonohydride, organoaluminum dihalide, organoaluminum dihydride, ororganoaluminum sesquihalide. The metal salt of the betadiketone of thecatalyst system can be obtained by uniting a beta-diketone with a metalselected from Groups II-A, III-A, IV-A, I-B, II-B, IV-B, V-B, VIB,VII-B, and VIII of the Periodic Table of the Elements reported in theHandbook of Chemistry and Physics, 45th edition, page B2, The ChemicalRubber Company (1964). Any alkene oxide can be homopolymerized orcopolymerized with another alkene oxide by means of the novel catalystof this invention. When one or more of the alkene oxides is unsaturated,the resulting rubbery polymer product is sulfur vulcanizable.

3,546,134 Patented Dec. 8, 1970 Accordingly, it is an object of thisinvention to provide an improved process of polymerizing alkene oxides.

Another object of this invention is to provide a novel catalyst systemfor polymerizing alkene oxides.

A further object of this invention is to provide a process ofpolymerizing alkene oxides wherein the monomer conversion is much higherthan the monomer conversion by the processes of the prior art.

Still another object of this invention is to produce rubbery alkeneoxide polymers which are flexible at low temperatures, and which arehighly resistant to the effects of high temperatures and to the effectsof ozone.

A still further object of this invention is to provide a process ofpolymerizing alkene oxides which Will result in the formation of arubbery polymer product which can be sulfur vulcanized.

These and other objects of the invention will become apparent to oneskilled in the art after studying the following detailed description andthe appended claims.

The novel catalyst system comprising an organoaluminum compound, a metalsalt of a beta-diketone, and Water can be employed for polymerizing anyalkene oxide. For example, alkene oxides containing up to and including20 carbon atoms, per molecule can be polymerized by the process of thisinvention. Generally, it is preferred that the alkene oxide monomercontain from about 2 to about 8 carbon atoms. Thus, alkene oxides whichcan be polymerized in accordance with this invention can be representedby the formula wherein R and R are selected from the group consisting ofhydrogen, saturated aliphatic, saturated cycloaliphatic, monoolefinicaliphatic, diolefinic aliphatic (conjugated and nonconjugated),monoolefinic cycloaliphatic, diolefinic cycloaliphatic (conjugated andnon conjugated), and aromatic radicals and combinations of these such asaralkyl, alkaryl, and the like. Some or all of the R and R radicals canbe halogen-substituted, and can contain oxygen in the form of an acyclicether linkage (O-) or an oxirane group Further, the alkene oxidesrepresented by the above formula can contain 1 or 2 olefinic linkages, lor 2 oxirane groups, and up to 1 ether linkage. In addition, both Rvariables can represent a divalent aliphatic hydrocarbon radical which,together with the carbon atoms of the oxirane group, can form acycloaliphatic hydrocarbon nucleus containing from about 4 to about 10carbon atoms and preferably from about 4 to about 8 carbon atoms.

Specific examples of some of the alkene oxides which are within theabove structural formula and which can be homopolymerized orcopolymerized in accordance with this invention are ethylene oxide(epoxyethane); 1,2- epoxypropane (propylene oxide); 1,2-epoxybutane;2,3- epoxybutane; 1,2-epoxypentane; 2,3-epoxypentane; 1,2- epoxyhexane;3,4-epoxyhexane; 1,2-epoxyheptane; 2,3- epoxyoctane;2,3-dimethyl-2,3-epoxypentane; 1,2-epoxy-4- methylpentane;2,3-epoxy-5-methylhexane; 1,2-epoxy-4,4- dimethylpentane;4,5-epoxyeicosane; 1-chloro-2,3-epoxypropane (epichlorohydrin);1-bromo-2,3-epoxypropane; 1,S-dichloro-Z,3-epoxypentane; 2iodo-3,4-ep0xybutane; styrene oxide; 6-oxabicyclo[3.1.0]hexane;7-oxabicyclo [4.1.0]heptane; 3 n-propyl-7-oxabicyclo[4.1.0]heptane;bis(2,3-epoxybutyl) ether; tert-butyl 4,5-epoxyhexyl ether; and2-phenylethyl 3,4-epoxybutyl ether.

Unsaturated alkene oxides within the above structural formula, includingethers, which can be homopolymerized or copolymerized with the saturatedalkene oxides include allyl 2,3-epoxypropyl ether (allyl glycidylether); allyl 3,4-epoxybutyl ether; l-methallyl 3,4-epoxyhexyl ether; 3-hexenyl 5,6-epoxyhexyl ether; 2,6-octadienyl 2,3,7,8-diepoxyoctyl ether;6-phenyl-3-hexenyl 3-ethyl-5,6-epoxyhexyl ether; 3,4-epoxy-1-butene(butadiene monoxide); 3,4-epoxy 1 pentene; phenyl-3,4-epoxy-l-pentene;1,2,9,IO-diepoxy-S-decene; 6,7-di-n-butyl-3,4,9,IO-diepoxy-1,11-dodecadiene; epoxy vinyl ether; allyl 2-methyl-2,3- epoxypropylether; 3-cyclohexyl-2-propenyl 4-cyclohexyl- 3,4 epoxybutyl ether; 2,4pentadienyl 2,3-diethyl-3,4- epoxybutyl ether; l-methallyl6-phenyl-3,4-epoxyhexyl ether; 5-(4-tolyl)2,3-epoxypentyl vinyl ether;bis[4-(3- cyclopentenyl)2,3-epoxybutyl] ether; 2-(2,4-cyclohexadienyl)ethyl 2,3-epoxybutyl ether; 2-(2,5-cyclohexadienyl) ethyl2-benzyl-4,5-epoxypentyl ether; 3,4-epoxy-1,5-hexadienyl isopropylether; allyl 3,4-dimethyl-3,4-epoxyhexyl ether;3,4-epoxy-4-(2,3-dimethylphenyl)l-butene;3,4-dimethyl-3,4-epoxy-l-pentene; 5 (4-methylcyclohexyl)3,4-epoxy-l-pentene; 4,5-diethyl-4,5-epoxy-2,6-octadiene; 4- (2,4cyclopentadienyl)1,2,6,7 diepoxyheptane; and 1-phenyl-l,2-epoxy-5,7-octadiene.

The novel catalyst of this invention comprises an organoaluminumcompound, a metal salt of a beta-diketone, and water. The organoaluminumcompound of the catalyst can be represented by the formula R" AlX WhereR" is a hydrocarbon radical selected from the group consisting ofsaturated aliphatic, saturated cycloaliphatic, and aromatic containingfrom 1 to carbon atoms, inclusive, and combinations such as alkaryl,aralkyl, and the like; X is a member of the class consisting ofhydrogen, fluorine, chlorine, bromine, and iodine; n is an integer offrom 1 to 3, inclusive; m is an integer of from 0 to 2, inclusive; andthe sum of the integers n and m equals 3. Organoaluminum compoundswithin the above formula include triorganoaluminum compounds,organoaluminum monohalides, organoaluminum monohydrides, organoaluminumdihalides, organoaluminum dihydrides, and organoaluminum sesquihalides.The organoaluminum sesquihalides as herein defined are intended to meana mixture of organoaluminum monohalides and organoaluminum dihalides ofthe formulas R AlX and RAlX respectively, wherein R is the same ashereinbefore defined with respect to the general formula and X is ahalogen. The organoaluminum sesquihalides can then be written as R Al Xor as R AlX Exemplary organoaluminum compounds within the above formulainclude trimethylaluminum, triethylaluminum, trim-butylaluminum,triisobutylaluminum, tri-n-hexylaluminum, tri-n-decylaluminum,tri-n-eicosylaluminum, tricycloheX- ylaluminum, triphenylaluminum,methyldiphenylaluminum, ethyldi(3,S-di-n-heptylphenyl)aluminum,tribenzylaluminum, tri 1 naphthylaluminum, di-n-octylphenylaluminum, tri4 tolylaluminum, dimethylchloroaluminum, methyldichloroaluminum,n-heptyldifiuoroaluminum, (3-ethylcyclopentyl) diiodoaluminum,methylisobutylchloroaluminum, diphenylbrornoaluminum,dibenzylchloroaluminum, di-n-octylchloroaluminum,n-octylphenylchloroaluminum, di n eicosyliodoaluminum,nbutyldihydroaluminum, methyldihydroaluminum, diisopropylhydroaluminum,ethylmethylhydroaluminum, diphenylhydroaluminum,benzyl-n-dodecylhydroaluminum, dicyclohexylhydroaluminum, 2,6 din-butyl-4-n-hexylphenyldihydroaluminum, and n-amylethylhydroaluminum.

The metal salt of the beta-diketone portion of the catalyst system canbe represented by the formula wherein Me is a metal selected from GroupsII-A, III-A, IV-A, I-B, II-B, lV-B, V-B, VI-B, VII-B, and VIII of thePeriodic Table of the Elements in the Handbook of Chemistry and Physics,45th edition, page 13-2, The Chemical Rubber Company (1964); each R' isa radical selected from the group consisting of saturated aliphatic,saturated cycloaliphatic, and aromatic containing from 1 to 10 carbonatoms, inclusive; and y is an integer equal to the valence of the metalMe (Moeller, Inorganic Chemistry, p. 241, Wiley and Sons, 1952).Preferred metals within the above groups include calcium, strontium,barium, copper, beryllium, magnesium, zinc, cadmium, mercury, boron,aluminum, gallium, indium, thallium, silicon, germanium, tin, lead,silver, vanadium, chromium, molybdenum, tungsten, manganese, iron,cobalt, nickel, zirconium, and titanium.

Specific beta-diketones which can be combined with a metal from theabove groups to form the corresponding metal salt include2,4-pentanedione(acetylacetone); 3,5- heptanedione;11,13-tricosanedione; l,3-dicyclohexyl-l,3- propanedione;1,S-dicyclopentyl-2,4-pentanedione; 1,3-diphenyl-1,3-propanedione;1,S-diphenyl-ZA-pentanedione; 2,8-dimethyl-4,6-nonanedione; 1,3di(4-n-butylphenyl) 1,3-propanedione; 1,11-diphenyl-5,7-hendecanedione;1- phenyl-l,3-butanedione; 2,4-decanedione; and1-(3,5-dimethylcyclohexyl)2,4-pentanedione.

The water which is employed as the third component of the catalyst ofthis invention assists in producing higher molecular weight rubberypolymers than are otherwise obtained. Although it is not actually knownjust how the Water functions in the polymerization reaction, the datashow the improved results obtained when water is employed in cooperationwith the organoaluminum compound and the metal salt of the beta-diketonecatalyst of the invention.

The alkene oxide polymerization reaction of this invention can beconducted either as a batch or as a continuous process with the novelcatalyst system being added in a single initial charge or inpredetermined increments during polymerization. The catalyst system canbe prepared by separately mixing the components and then charging themixture in a manner as hereinbefore described or the catalyst componentscan be separately charged. Similarly, the alkene oxide monomers can beintroduced into the reaction zone in one charge or they can be addedgradually during polymerization. In order to expedite and improve theefiiciency of the polymerization reaction, it is generally preferredthat the reaction be conducted in the presence of an inert diluent.Suitable diluents which can be used for this purpose include parafiinic,cycloparaflinic, and aromatic hydrocarbons containing from about 4 toabout 10 carbon atoms per molecule. Exemplary diluents which can be usedare butane, pentane, hexane, decane, cyclopentane, cyclohexane,methylcyclohexane, benzene, toluene, xylene, ethylbenzene, and the like.It is also within the spirit and scope of this invention to employhalogenated hydrocarbons as diluents. Diluents within this class includechlorobenzene and the like. Since the actual diluent employed is largelya matter of choice, it is obviously possible to employ other diluentsthan those herein identified without departing from the spirit and scopeof the invention. It is also possible to employ mixtures of two or moresuitable compounds as diluents.

The amount of catalyst used for effecting polymerization of the alkeneoxides can vary over a rather broad range. The catalyst level ispreferably and for convenience determined on the basis of theorganoaluminum compound in the catalyst system. As a general rule, theamount of catalyst is maintained within the range of about 1 to aboutgram millimoles of organoaluminum compound per 100 grams of monomerbeing polymerized and preferably in the range of about 5 to about 40gram millimoles of organoaluminum compound per 100 grams of monomer. Inthe copolymeriza'tion of two or more alkene oxide monomers, the amountof catalyst is based on the total amount of alkene oxide monomers.

The metal salt of the beta-diketone employed in the catalyst system isbased on the amount of organoaluminum compound present. Generally, themole ratio of the metal salt of the beta-diketone to the organoaluminumcompound is within the range of about 0.01:1 to about 0.5 :1 andpreferably within the range of about 0.03:1 to about 0.3:1. Obviously,the metal salt can be used in amounts outside of the range recitedwithout departing from the scope of the invention.

The quantity of water employed in the catalyst system is also based onthe organoaluminum component. Generally, the water is present in thecatalyst system in an amount within the range of about 0.02 to about 1.6moles per mole of organoaluminum compound and preferably within therange of about 0.1 to about 1 mol per mol of organoaluminum compounds.

The temperature and pressure at which the polymerization reaction ofthis invention is effected can vary over a rather wide range. Generally,the reaction is conducted at a temperature within the range of about 40to about 250 F. and preferably within the range of about 85 to about 200F. Polymerization is usually conducted at a pressure which will maintainthe materials substantially completely in the liquid state. Obviously,the reaction can be conducted at superatmospheric pressures of severalthousand pounds if desired.

The duration of the reaction will depend primarily upon temperature,pressure, and the activity of the particular catalyst being used.Usually, the process will be conducted for a period of from about a fewminutes or less to about 100 hours or more. A preferred range is fromabout 10 minutes to about 50 hours. Termination of the reaction, removalof catalyst, recovery of polymer, and so on, can be carried out in aconventional manner.

The alkene oxide polymers produced in accordance with the novel catalystsystem of this invention exhibit extremely good low temperatureflexibility. The polymers are particularly resistant to the effects ofheat and tothe eifects of ozone. The polymers have unlimited utility inthe automobile industry for fabricating articles such as motor mounts,body mounts, suspension system parts, hoses, tubing, and the like.

The following examples will serve to illustrate the improved resultsobtained by polymerizing alkene'oxides with the novel catalyst system ofthis invention. It must be understood that such'examples are for thepurpose of illustration only, and that many variations and modificationscan be made from the various examples by one skilled in the art withoutdeparting from the concept of the invention.

EXAMPLES 1-24 A series of runs was conducted whereby 1,2-epxypropane waspolymerized by means of a catalyst comprising triisobutylaluminum,various metal salts of 2,4-pentanedione, and water. Variable quantitiesof water were used to illustrate the operability of the invention over arather broad range. Control runs without water were made in order toillustrate the improved result obtained by water in cooperation with theorganoaluminum compound and the metal salt of the 2,4-pentanedione. Thematerials were charged to a reactor in the following proprotions:

1,2-epoxypropane, parts by weight 100 Cyclohexane, parts by weight 780Triisobutylaluminum (TBA) mhm. 30 Metal salt of 2,4-pentanedione, mhm. 15 Water, mhm. 1 variable Metal salt:TBA mole ratio 0.17:1 Temperature, F158 Time, hours 7 1 Gram millimoles per 100 grams monomer.

The actual polymerization technique employed involved the steps ofcharging the reactor with cyclohexane and thereafter purging it withnitrogen. The 1,2-epoxypropane was then charged to the reactor followedby the triisobutylaluminum and the water. The metal salt of the2,4-pentanedione was then charged to the reactor, and polymerizationallowed to continue for the period indicated. At the termination of eachrun, the viscosity of the reaction mixture was reduced by chargingacetone to the reactor. The mixture was then poured into water which hadpreviously been acidified with hydrochloric acid. The mixture was thenallowed to settle to form an aqueous phase and an organic phase. Theaqueous phase was separated and removed. Approximately one weightpercent, based on the polymer, of2,2-methylene-bis(4-methyl-6-tertbutylphenol) antioxidant was added tothe organic phase and the polymer recovered from it by evaporating thediluent. The polymer thus recovered was dried under vacuum. Table 1below illustrates the properties of each of the polymers produced bymeans of the different catalyst systems employed.

TABLE I Monomer Water, Mole ratio, conversion, Inherent Example No.Metal salt of beta-diketone mhm. H2O :TBA percent viscosity 0 ontrolZinc acetylacetonate (Zn' 0 1 .110 5 0.17:1 10 0. 33: 1 l5 0. 5: 1 do 301:1

Cupric acetylacetonate (Cu++) 0 0 10 0.33:1 0. 5: 1 0. 67 1 Vanadiumacetylacetonate (V'*) 0 .do..... 10 0.33:1 15 0. 5:1

1 Gram mlllimoles per grams monomer.

In order to determine the inherent viscosity, one-tenth gram of polymerwas placed in a wire cage made from SO-mesh screen and the cake wasplaced in 100 ml. of toluene contained in a wide-mouth, 4-ounce bottle.After standing at room temperature (approximately 77 F.) for about 24hours, the cage was removed and the solution filtered throuh a sulfurabsorpttion tube of Grade C porosity to remove any solid particlespresent. The resulting solution was run through a Medalia typeviscometer supported in a 77 F. bath. The viscometer was previouslycalibrated with toluene. The relative viscosity is the ratio of theviscosity of the polymer solution to that of toluene. The inherentviscosity is calculated by dividing the natural logarithm of therelative viscosity by the weight of the soluble portion of the originalsample.

It can be seen from these data that the catalyst system comprising theorganoaluminum compound the metal salt of the beta-diketone, and thewater is superior to the catalyst system comprising only theorganoaluminum compound and the metal salt of the beta-diketone in thesense that the percent monomer conversion is much higher. All of thepolymers produced by the catalyst Cit the beta-diketone, and the water.The materials were charged to a reactor in the following proportions:

Epichlorohydrin, parts by weight 100 Toluene, parts by weight 860Triisobutylaluminum, mhm. 30

Metal salt of 2,4-pentanedione, mhm. variable Water, mhm. 20 H OzTBAmole ratio 0.67:1 Temperature, F. 122 Time, hours 20 Gram millimoles per100 grams monomer.

TAB LE II Metal salt of 2,4-pentanedlone Monomer Water, Mole ratio,conversion, Example No. Type MhmJ mhm. 1120: A percent Control Cobaltacetylacetonate (00 6 20 26 o 6 20 0.67:1 100 Control... Zineaeetylacetonate (Zn 6 26 27 o 0. 67:1 50 28 do G 20 0.67:1 105 Contrconium aeetylacetonate (Zr 6 44 d0 G 20 0.67:1 78

l Gram mlllimoles per 100 grams monomer.

system of this invention were observed to be gel-free, high molecularweight rubbers.

EXAMPLE Allyl glycidyl ether was copolymerized with 1,2-epoxypropane bymeans of a catalyst system comprising triisobutylaluminum, zinc salt of2,4-pentanedione, and water. The materials were charged to a reactor inthe following proportions:

Gram millimoles per 100 grams monomer.

The technique employed for effecting the copolymerization reaction wasthe same as the technique followed and described in Examples l-24. Thecopolymer produced was a high molecular weight rubber. This exampleillustrates the operability and the improved result obtained by thecatalyst system of this invention for forming a copolymer.

EXAMPLES 2629 A series of runs was conducted whereby epichlorohydrin waspolymerized by means of a catalyst system comprisingtriisobutylaluminum, various metal salts of 2,4-pentanedione, and water.Control runs were made without water in order to illustrate the improvedand unexpected result obtained with the catalyst system comprising theorganoaluminum compound, the metal salt of EXAMPLES 30-35 A series ofruns was conducted whereby epichlorohydrin was copolymerized with1,2-epoxypropane (propylene oxide) by means of a catalyst comprisingtriisobutylaluminum, zinc salt of 2,4-pentanedione, and water. Thematerials were charged to a reactor as follows:

Epichlorohydrin, parts by weight variable Propylene oxide, parts byweight variable Toluene, parts by weight 860 Triisobutylaluminum, mhm.30

Zinc salt of 2,4-pentanedione, mhm. 6

Water, mhm. 20 Zn saltzTBA mole ratio 0.2:1 H OsTBA mole ratio 0.67:1Temperature, F. variable Time, hours 24 Gram mlllimoles per 100 gramsmonomer.

The technique used for copolymerizing the epichlorohydrin and1,2-epoxypropane was the same as that used in Examples 1-24. All of thecopolymers produced were high molecular weight rubbers. The resultsobtained from these runs are reported in Table III below.

TABLE III Ratio of epichlorohydrin to 1,2- Temperepoxy- Monomer ature,propane, conversion, F. by weight percent Example No.:

EXAMPLES 36 and 37 Two runs were made whereby epichlorohydrin waspolymerized by means of a catalyst comprising triisobutylaluminum, zincsalt of 2,4-pentanedione, and water. The quantities of the catalyst usedwere varied between the two runs in order to illustrate the utility ofthe invention with different catalyst concentrations. The polymerizationreactions were conducted in toluene, using 860 parts by weight oftoluene for each 100 parts by weight of epichlorohydrin monomer.Polymerization was conducted at 10 wherein Me is a metal selected fromGroups II-A, IIIA, IVA, I-B, II-B, IV-B, VB, VI-B, VII-B and VIII of thePeriodic Table; each R' is a radical selected from the group consistingof saturated aliphatic, saturated cycloaliphatic and aromatic config ixgs gzs g gg g g d 525 5 3232233 233 taming from 1 to carbon atoms,inclusive; and y Examples 1-24. The results obtained are presented in gInteger equal to the valence of the metal Me; Table IV below. a

TABLE IV Zinc salt of 2,4- Triisopentanedione or P lym ylacetylacetonenation Monomer aluminum, H2O, time, conversion, Inherent mhm. Type Mhm.h ,1 hours percent viscosity Example No.:

1 Gram millimoles per 100 grams monomer.

The epichlorohydrin polymer produced by the catalyst 20 (c) Wat Whef6iIl the H1016 ratio of themetal Salt of Examples 36 and 37 was a highmolecular weight of the beta-drketone to the organoaluminum commbber.The inherent viscosity was determined in the pound is within the rangeof about 0.01:1 to about same manner as that described in connectionwith 05:1 and wherein the water is present in an amount Examples 1-24.It can be seen from these data that the wrthm the range of about 0.02 toabout 1.6 moles catalyst of this invention can be used for polymerizingper mole of organoaluminum compound.

epichlorohydrin.

As hereinbefore indicated, any unsaturated alkene oxide can behomopolymerized or copolymerized with a saturated or unsaturated alkeneoxide to form a rubbery polymer which can be sulfur vulcanized. Althoughthe examples herein presented illustrate the copolymerization of1,2-epoxypropane with allyl glycidyl ether and with epichlorohydrin, itis obvious that the invention is not intended to be limited thereto. Forexample, the catalyst of this invention can be used to form a copolymerof epichlorohydrin and allyl glycidyl ether. In the copolymerization oftwo unsaturated alkene oxides with the novel catalyst system of thisinvention, it is generally preferred to form a copolymer of allyl2,3-epoxypropyl ether (allyl glycidyl ether) and 3,4-epoxy-1-butene(butadiene monoxide). These copolymers can be freely sulfur vulcanizedbecause the polymer chains contain a multiplicity of olefinic bonds.

Although the invention has been described in considerable detail, itmust be understood that such detail is for the purpose of illustrationonly and that many variations and modifications can be made by oneskilled in the art without departing from the spirit and scope of theinvention.

We claim:

1. A catalyst consisting essentially of (a) at least one organoaluminumcompound of the formula R",,AIX

wherein R" is a hydrocarbon radical selected from the group consistingof saturated aliphatic, saturated cycloaliphatic and aromatic containingfrom 1 to 20 carbon atoms, inclusive; X is selected from the classconsisting of hydrogen, fluorine, chlorine, bromine and iodine; n. is aninteger of from 1 to 3, inclusive, m is an integer of from 0 to 2,inclusive; and the sum of the integers n and m equals 3;

(b) a metal salt of a beta-diketone having the formula 2. A catalystaccording to claim 1 wherein the mole ratio of the metal salt of thebeta-diketone to the organoaluminum compound is within the range ofabout 0.03:1 to about 0.321; and wherein the water is present in anamount within the range of about 0.1 to about 1.0 mole per mole oforganoaluminum compound.

3. A catalyst system according to claim 2 wherein said organoaluminumcompound is selected from the group consisting of triorganoaluminums,organoaluminum monohalides, organoaluminum monohydrides, organoaluminumdihalides, organoaluminum dihydrides, and organoaluminum sesquihalides.

4. A catalyst system according to claim 1 wherein said organoaluminumcompound is triisobutylaluminum.

5. A catalyst system according to claim 4 wherein said metal salt of abeta-diketone is selected from the group consisting-of zincacetylacetonate, cupric acetylacetonate, zirconium acetylacetonate,vanadic acetylacetonate, manganous acetylacetonate, manganicacetylacetonate, ferrous acetylacetonate, and cobaltous acetylacetonate.

6. A catalyst system according to claim 2 wherein said organoaluminumcompound is triisobutylaluminum.

7. A catalyst system according to claim 6 wherein said metal salt of abeta-diketone is selected from the group consisting of zincacetylacetonate, cupric acetylacetonate, zirconium acetylacetonate,vanadic acetylacetonate, manganous acetylacetonate, manganicacetylacetonate, ferrous acetylacetonate, and cobaltous acetylacetonate.

References Cited UNITED STATES PATENTS 2,866,761 12/1958 Hill et al.252431X 3,219,591 11/1965 Vandenberg 252-431 3,267,076 8/ 1966 Ishii eta1 252431X 3,385,800 5/1968 Furukawa et a1. 260-2 3,459,721 8/1969 Kuntzet al. 252431X 3,462,406 8/ 1969 Natta et al 252-43l X PATRICK P.GARVIN, Primary Examiner US. Cl. X.R.

